Method for producing alcohol compound

ABSTRACT

Disclosed is a practical method for efficiently producing an alcohol compound by hydrogenating an aldehyde by using a homogeneous copper catalyst which is an easily-available low-cost metal species. Specifically disclosed is a method for producing an alcohol compound, which is characterized in that a hydrogenation reaction of an aldehyde compound is performed in the presence of a homogeneous copper catalyst and a diphosphine compound.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a National Stage of International Application No.PCT/JP2008/072540 filed Dec. 11, 2008, the contents of all of which areincorporated herein by reference in their entirety.

TECHNICAL FIELD

The present invention relates to a method for producing an alcoholcompound, and more specifically to a method for producing an alcoholcompound by performing a hydrogenation reaction of an aldehyde compoundin the presence of a homogeneous copper catalyst and a diphosphinecompound.

BACKGROUND ART

Conventionally, alcohol compounds have been widely used as components orsynthetic intermediates and the like for various pharmaceuticals,agricultural chemicals, flavors, fragrances, or commodity chemicals. Asmethods for producing such alcohol compounds, methods by which analcohol compound is obtained by hydrogenation of an aldehyde compoundhave been known to be useful methods. In this connection, variouscatalysts and reaction modes have been proposed for the hydrogenationreaction. A method by which, among aldehyde compounds, anα,β-unsaturated aldehyde is selectively hydrogenated to obtain an allylalcohol is said to be particularly useful.

As methods for obtaining an alcohol compound by a heterogeneous catalystreaction in which an aldehyde compound is hydrogenated, methods havebeen known which use an iridium catalyst, an osmium catalyst, apalladium catalyst, a nickel catalyst, a platinum catalyst, a rutheniumcatalyst, or the like, as described in Non-Patent Document 1 andNon-Patent Document 2, for example. However, these methods oftenrequires harsh reaction conditions such as high temperature or highpressure, and are severely limited in terms of operability, productionapparatus, and the like. Moreover, particularly in the cases where anα,β-unsaturated aldehyde is used as the hydrogenation substrate, thereis a problem that the selectivity is generally low.

Meanwhile, as methods for obtaining an alcohol compound by a homogeneouscatalyst reaction in which an aldehyde compound is hydrogenated, methodswhich use a complex using a platinum group metal and other methods havebeen known (for example, see Non-Patent Document 3 and Patent Document1). However, such a complex uses a platinum group metal, which isexpensive. Hence, there are problems from the economical view point thatthe complex is expensive and that the influence of fluctuation of theprice of a metal of interest is large. Moreover, there is a problemthat, when an α,β-unsaturated aldehyde is used as the hydrogenationsubstrate, iridium complexes, rhodium complexes, and osmium complexeshave low selectivity.

In recent years, a method has been reported in which an aldehyde ishydrogenated by use of a catalyst made of a copper compound anddimethylphenylphosphine (Non-Patent Document 4). However, there is aproblem of operability because it is necessary to usedimethylphenylphosphine, which is unstable in the air, and highlysmells, in an excessive amount with respect to copper. In addition,there also is a problem of cost effectiveness because the catalyticactivity is low, and consequently it is necessary to use a large amountof the catalyst (2 to 5 mol % in terms of Cu). Meanwhile, in Non-PatentDocument 4, a method is developed which uses [(tripod)CuH]₂ as thecatalyst, also. However, the method has the following problem.Specifically, since the catalytic activity is extremely low, it isnecessary to use a tridentate ligand Tripod in an excessive amount withrespect to copper for the reaction to be completed, even when thecatalyst is used at 2.5 mol % with respect to the substrate. Inaddition, there is a problem of operability because the range ofpressure for the reaction to proceed is from 50 to 70 psi (approximately0.35 to 0.5 MPa), which is extremely narrow.

Note that, in Patent Document 2 and Non-Patent Document 5, a catalystfor a homogeneous asymmetric hydrogenation reaction has been developedusing a copper catalyst. However, this is a method for obtaining anoptically active compound by hydrogenating a ketone moiety or a doublebond of a prochiral unsaturated compound, and neither Patent Document 2nor Non-Patent Document 5 describes hydrogenation of aldehydes.

-   Patent Document 1: Japanese Patent Application Publication No. Hei    08-225467-   Patent Document 2: International Patent Application Publication No.    WO2007/007646.-   Non-Patent Document 1: Handbook of Heterogeneous Hydrogenation,    Ertl, G.; Knozinger, H.; Weitkamp, J. Eds., VCH Weinheim, 1997, p.    2186.-   Non-Patent Document 2: Muroi, Takashiro, “KOUGYOU KIKINZOKU SHOKUBAI    (Industrial Noble Metal Catalyst),” 2003, p. 111.-   Non-Patent Document 3: Handbook of Homogeneous Hydrogenation, de    Vries, J. G.; Elsevier, C. J. Eds., Wiley-VCH Weinheim, 2007,    Vol. 1. p. 413.-   Non-Patent Document 4: Chen, J.-X.; Daeuble, J. F.; Bresdensky, D.    M.; Stryker, J. M. Tetrahedron 2000, 56, 2153.-   Non-Patent Document 5: Shimizu, H.; Igarashi, D.; Kuriyama, W.;    Yusa, Y.; Sayo, N.; Saito, T. Org. Lett. 2007, 9, 1655.

DISCLOSURE OF THE INVENTION Problem to be Solved by the Invention

An object of the present invention is to provide a practical method forefficiently producing an alcohol compound by hydrogenating an aldehydeby using a homogeneous copper catalyst which is an easily-availablelow-cost metal species.

Means for Solving the Problem

In view of the above described circumstances, the present inventor hasconducted earnest study. As a result, the present inventor has found amethod for producing an alcohol compound at a high yield and at a highcatalytic efficiency, by performing a hydrogenation reaction of analdehyde compound in the presence of a homogeneous copper catalyst and adiphosphine compound. This finding has led to the completion of thepresent invention.

Specifically, the present invention provides a method for producing analcohol compound, characterized by performing a hydrogenation reactionof an aldehyde compound in the presence of a homogeneous copper catalystand a diphosphine compound.

Note that, in the present invention, “homogeneous” means a state wherethe catalyst used is substantially dissolved during the hydrogenationreaction, and a state where the catalyst used is dissolved ordissolvable during the hydrogenation reaction. The “homogeneous” means astate where the catalyst is dissolved depending on the kinds of ahydrogenation substrate and a solvent used, the reaction conditions suchas reaction temperature, and the like. This state, for example, includesa case where the catalyst used is dissolved with the increase of thereaction temperature, and similar cases. Moreover, the “homogeneous”means a case where characteristics of the reaction system hardly changeat the interface, and are uniform over the entirety, that is, a statewhere the catalyst having a catalyst activity in the reaction system isdissolved or dissolvable in a solution, where the hydrogenationsubstrate used for the homogeneous hydrogenation reaction, an additiveused if necessary, a deactivated catalyst, or the like may be present assolid.

Effects of the Invention

According to the production method of the present invention, it ispossible to produce an alcohol compound from an aldehyde compound at ahigh yield and at a high catalytic efficiency.

BEST MODES FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

A method for producing an alcohol compound of the present invention ischaracterized by performing a hydrogenation reaction of an aldehydecompound in the presence of a homogeneous copper catalyst and adiphosphine compound.

In the present invention, an aldehyde compound is used as ahydrogenation substrate, which is a raw material. As the aldehydecompound used as the hydrogenation substrate, various kinds of aldehydescan be used. For example, those represented by the following generalformula (2) and the like can be used as appropriate:R—CHO  (2)(where R represents an aryl group which may have a substituent, aheterocyclic group which may have a substituent, or a saturated orunsaturated, chain or cyclic hydrocarbon group which may have asubstituent).

Examples of the aryl group represented by R in the formula (2) includearomatic monocyclic and aromatic polycyclic groups such as a phenylgroup, a naphthyl group, an anthryl group, a phenanthryl group, and anindenyl group. Moreover, the examples also include metallocenyl groupssuch as a ferrocenyl group.

Examples of the heterocyclic group represented by R in the formula (2)include heteromonocyclic or heteropolycyclic groups such as a furylgroup, a thienyl group, a pyridyl group, a pyrimidinyl group, apyrazinyl group, a pyridazinyl group, a pyrazolyl group, an imidazolylgroup, an oxazolyl group, a thiazolyl group, a benzofuryl group, abenzothienyl group, a quinolyl group, an isoquinolyl group, aquinoxalinyl group, a phthalazinyl group, a quinazolinyl group, anaphthyridinyl group, a cinnolinyl group, a benzoimidazolyl group, abenzoxazolyl group, and a benzothiazolyl group.

Examples of the saturated or unsaturated, chain or cyclic hydrocarbongroup represented by R in the formula (2) include alkyl groups such as amethyl group, an ethyl group, a n-propyl group, an isopropyl group, an-butyl group, an isobutyl group, a s-butyl group, a t-butyl group, apentyl group, a hexyl group, a heptyl group, and an octyl group;cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, acyclopentyl group, and a cyclohexyl group; and groups of unsaturatedhydrocarbons and the like, such as a benzyl group, a vinyl group, and amethallyl group.

Here, each of the aryl group, the heterocyclic group, and thehydrocarbon group may have a substituent. Examples of the substituentinclude alkyl groups, alkenyl groups, aryl groups, alaryl groups,alicyclic groups, halogen atoms, a hydroxy group, alkoxy groups, acarboxyl group, ester groups, an amino group, dialkylamino groups,heterocyclic groups, and the like.

Here, examples of the alkyl group as the substituent include linear orbranched alkyl groups having, for example, 1 to 15 carbon atoms,preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbonatoms. Specific examples thereof include a methyl group, an ethyl group,a n-propyl group, an isopropyl group, a n-butyl group, a s-butyl group,an isobutyl group, a t-butyl group, a n-pentyl group, a neopentyl group,a n-hexyl group, and the like.

Examples of the alkenyl group as the substituent include alkenyl groupshaving, for example, 2 to 10 carbon atoms, and specific examples thereofinclude a vinyl group, a 2-propenyl group, and the like.

Examples of the aryl group as the substituent include aryl groupshaving, for example, 6 to 14 carbon atoms, and specific examples thereofinclude a phenyl group, a naphthyl group, an anthryl group, aphenanthryl group, a biphenyl group, and the like.

Examples of the alaryl group as the substituent include a benzyl group,a 1-phenylethyl group, and the like.

Examples of the alicyclic group as the substituent include cycloalkylgroups having 5 to 8 carbon atoms such as a cyclopentyl group, acyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

Examples of the halogen atom as the substituent include a fluorine atom,a chlorine atom, a bromine atom, and an iodine atom.

Examples of the alkoxy group as the substituent include linear orbranched alkoxy groups having, for example, 1 to 6 carbon atoms, andspecific examples thereof include a methoxy group, an ethoxy group, an-propoxy group, an isopropoxy group, a n-butoxy group, a s-butoxygroup, an isobutoxy group, a t-butoxy group, a n-pentyloxy group, aneopentyloxy group, a n-hexyloxy group, and the like.

Examples of the ester group as the substituent include alkyloxy carbonylgroups having 2 to 6 carbon atoms such as a methoxycarbonyl group and anethoxycarbonyl group; aryloxy carbonyl groups having 6 to 10 carbonatoms such as a phenoxycarbonyl group; and the like.

Examples of the dialkylamino group as the substituent include a dimethylamino group, a diethylamino group, and the like.

Examples of the heterocyclic group as the substituent include aliphaticheterocyclic groups and aromatic heterocyclic groups. Examples of thealiphatic heterocyclic groups include 5- to 8-membered, preferably 5- or6-membered, monocyclic, polycyclic, or fused polycyclic aliphaticheterocyclic groups which have, for example, 2 to 14 carbon atoms, andwhich contain, as their hetero atoms, at least one, preferably 1 to 3hetero atoms such as nitrogen atoms, oxygen atoms, and sulfur atoms.Specific examples of the aliphatic heterocyclic groups include a2-oxopyrrolidyl group, a piperidino group, a piperazinyl group, amorpholino group, a tetrahydrofuryl group, a tetrahydropyranyl group, atetrahydrothienyl group, and the like. Meanwhile, examples of thearomatic heterocyclic groups include 5- to 8-membered, preferably 5- or6-membered, monocyclic, polycyclic, or fused polycyclic aromaticheterocyclic (heteroaryl) groups which have, for example, 2 to 15 carbonatoms, and which contain, as their hetero atoms, at least one,preferably 1 to 3 hetero atoms such as nitrogen atoms, oxygen atoms, andsulfur atoms. Specific examples of the aromatic heterocyclic groupsinclude a furyl group, a thienyl group, a pyridyl group, a pyrimidinylgroup, a pyrazinyl group, a pyridazinyl group, a pyrazolyl group, animidazolyl group, an oxazolyl group, a thiazolyl group, a benzofurylgroup, a benzothienyl group, a quinolyl group, an isoquinolyl group, aquinoxalyl group, a phthalazinyl group, a quinazolinyl group, anaphthyridinyl group, a cinnolinyl group, a benzoimidazolyl group, abenzoxazolyl group, a benzothiazolyl group, and the like.

These substituents may be substituted with another substituent.

In addition, when R in the aldehyde compound used in the presentinvention is an unsaturated hydrocarbon group, i.e., when, for example,an α,β-unsaturated aldehyde compound represented by a general formula(3) is used as appropriate, the α,β-unsaturated aldehyde can beselectively hydrogenated, so that the corresponding allyl alcohol can beobtained:

(where R⁵ to R⁷ each independently represent a hydrogen atom, an alkylgroup which has 1 to 10 carbon atoms and which may have a substituent,an alicyclic group which has 5 to 8 carbon atoms and which may have asubstituent, an alkenyl group which may have a substituent, an arylgroup which may have a substituent, or a heterocyclic group which mayhave a substituent; and R⁵ and R⁶, as well as R⁵ and R⁷, may be bondedto each other to form a ring).

Examples of the alkyl group having 1 to 10 carbon atoms and representedby R⁵ to R⁷ in the formula (3) include alkyl groups having 1 to 10carbon atoms such as a methyl group, an ethyl group, a n-propyl group,an isopropyl group, a n-butyl group, an isobutyl group, a s-butyl group,a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octylgroup, a nonyl group, and a decyl group.

Examples of the alicyclic group having 5 to 8 carbon atoms andrepresented by R⁵ to R⁷ in the formula (3) include cycloalkyl groupshaving 5 to 8 carbon atoms such as a cyclopentyl group, a cyclohexylgroup, a cycloheptyl group, and a cyclooctyl group.

Examples of the alkenyl group represented by R⁵ to R⁷ in the formula (3)include a vinyl group, a 2-propenyl group, and the like.

Examples of the aryl group represented by R⁵ to R⁷ in the formula (3)include aromatic monocyclic or aromatic polycyclic groups such as aphenyl group, a naphthyl group, an anthryl group, a phenanthryl group,and an indenyl group. The examples also include metallocenyl groups suchas a ferrocenyl group.

Examples of the heterocyclic group represented by R⁵ to R⁷ in theformula (3) include heteromonocyclic or heteropolycyclic groups such asa furyl group, a thienyl group, a pyridyl group, a pyrimidinyl group, apyrazinyl group, a pyridazinyl group, a pyrazolyl group, an imidazolylgroup, an oxazolyl group, a thiazolyl group, a benzofuryl group, abenzothienyl group, a quinolyl group, an isoquinolyl group, aquinoxalinyl group, a phthalazinyl group, a quinazolinyl group, anaphthyridinyl group, a cinnolinyl group, a benzoimidazolyl group, abenzoxazolyl group, and a benzothiazolyl group.

Here, each of the alkyl groups, the alicyclic groups, the alkenylgroups, the aryl groups, and the heterocyclic groups may have asubstituent. Examples of the substituent include alkyl groups, alkenylgroups, aryl groups, alaryl groups, alicyclic groups, halogen atoms, ahydroxy group, alkoxy groups, a carboxyl group, ester groups, an aminogroup, dialkylamino groups, heterocyclic groups, and the like.

Here, the substituent is the same as that described for R in the generalformula (2).

Meanwhile, when R⁵ and R⁶, or R⁵ and R⁷ are bonded to each other toforma ring, examples of the ring include those in which R⁵ and R⁶together form an alkylene group having 4 to 6 carbon atoms such as atetramethylene group, a pentamethylene group, and a hexamethylene group;and those in which R⁵ and R⁷ together form an alkylene group having 3 to5 carbon atoms such as a trimethylene group, a tetramethylene group, anda pentamethylene group.

In the present invention, when R is an aryl group which may have asubstituent or a heterocyclic group which may have a substituent,specific examples of the aldehyde compound of the above-describedgeneral formula (2) include benzaldehyde, p-tolylaldehyde,cuminaldehyde, salicylaldehyde, anisaldehyde, o-methoxy benzaldehyde,o-methoxy cinnamic aldehyde, vanillin, ethyl vanillin,3,4-dimethoxybenzaldehyde, piperonal, helional, phenoxyacetaldehyde,p-methylphenoxyacetaldehyde, furfural, 5-methylfurfural,5-hydroxymethylfurfural, pyridinecarboxaldehyde,thiophenecarboxaldehyde, and the like.

Meanwhile, in the present invention, when R is a saturated orunsaturated, chain or cyclic hydrocarbon group, specific examples of thealdehyde compound of the general formula (2) include acetaldehyde,propionaldehyde, n-valeraldehyde, isovaleraldehyde, 2-methylbutanal,n-hexanal, n-heptanal, n-octanal, n-nonanal, 2-methyloctanal,3,5,5-trimethylhexanal, decanal, undecanal, 2-methyldecanal, dodecanal,2-methylundecanal, tridecanal, tetradecanal, citronellal, caryophyllenealdehyde, phenylacetaldehyde, p-methylphenylacetaldehyde,p-isopropylphenylacetaldehyde, hydratropaldehyde,p-methylhydratropaldehyde, phenylpropionaldehyde,3-methyl-5-phenylvaleraldehyde, phenoxyacetaldehyde,p-methylphenoxyacetaldehyde, β-methylhydrocinnamic aldehyde, cyclamenaldehyde, p-ethyldimethylhydrocinnamic aldehyde,p-isobutyl-α-dimethylhydrocinnamic aldehyde,p-tert-butyl-α-dimethylhydrocinnamic aldehyde, and the like.

Moreover, in the present invention, specific examples of theα,β-unsaturated aldehyde compound of the general formula (3) includecrotonaldehyde, β-methylcrotonaldehyde, 2-pentenal, trans-2-hexenal,trans-2-heptenal, trans-2-octenal, trans-2-nonenal, trans-2-decenal,trans-2-undecenal, trans-2-tridecenal, 2,4-hexadienal, 2,4-heptadienal,2,4-octadienal, 2,4-nonadienal, 2,6-nonadienal, 2,4-decadienal,trimethyldecadienal, citral, geranial, neral, perillaldehyde, safranal,myrtenal, cinnamic aldehyde, α-methyl cinnamic aldehyde,4-methyl-2-phenyl-2-pentenal, 5-methyl-2-phenyl-2-hexenal, α-amylcinnamic aldehyde, α-hexyl cinnamic aldehyde, o-methoxy cinnamicaldehyde, β-phenyl cinnamic aldehyde, furylacrolein, and the like.

In the present invention, a homogeneous copper catalyst is used in thereaction system. The homogeneous copper catalyst is not particularlylimited, as long as the reduction reaction of the present inventionproceeds. For example, a homogeneous copper catalyst which can berepresented by the following general formula (4) can be used:[Cu(X)_(l)(L)_(m)]_(n)  (4)(where X represents a hydrogen atom, a halogen atom, an alkyl group, anaryl group, an alkoxy group, a carboxyl group, a triflate group, anitrile group, dimethylformamide, NO₃, SO₄, CO₃, BF₄, or BH₄; Lrepresents a monophosphine ligand; l represents an integer of 1 or 2; mrepresents 0 to 3; and n represents a natural number).

Examples of the halogen atom represented by X in the general formula (4)include a fluorine atom, a chlorine atom, a bromine atom, and an iodineatom.

Examples of the alkyl group represented by X in the general formula (4)include alkyl groups such as a methyl group, an ethyl group, a n-propylgroup, an isopropyl group, a n-butyl group, an isobutyl group, a s-butylgroup, a t-butyl group, a pentyl group, a hexyl group, a heptyl group,and an octyl group.

Examples of the aryl group of X in the general formula (4) includearomatic monocyclic or aromatic polycyclic groups such as a phenylgroup, a naphthyl group, an anthryl group, a phenanthryl group, anindenyl group, and a mesityl group; and the like.

Examples of the alkoxy group represented by X in the general formula (4)include a methoxy group, an ethoxy group, a propoxy group, an isopropoxygroup, a n-butoxy group, a t-butoxy group, a phenoxy group, a benzyloxygroup, and the like.

Examples of the carboxyl group represented by X in the general formula(4) include a formyloxy group, an acetoxy group, a propionyloxy group, abutyryloxy group, a benzoyloxy group, and the like.

The monophosphine compound represented by L in the general formula (4)can be represented by the following general formula (5):

(where R⁸ to R¹⁰ each independently represent an alkyl group having 1 to10 carbon atoms, an alicyclic group which has 5 to 8 carbon atoms andwhich may have a substituent, an aryl group which may have asubstituent, or a heterocyclic group which may have a substituent; andany two of R⁸, R⁹, and R¹⁰ may be bonded to each other to form a ring).

Examples of the alkyl group having 1 to 10 carbon atoms and representedby R⁸ to R¹⁰ in the general formula (5) include linear or branched alkylgroups having 1 to 10 carbon atoms, and examples thereof include amethyl group, an ethyl group, a n-propyl group, an isopropyl group, an-butyl group, an isobutyl group, a s-butyl group, a t-butyl group, an-pentyl group, a n-hexyl group, a n-octyl group, and the like.

Examples of the alicyclic group having 5 to 8 carbon atoms andrepresented by R⁸ to R¹⁰ in the general formula (5) include acyclopentyl group, a cyclohexyl group, a cycloheptyl group, and thelike.

Examples of the aryl group represented by R⁸ to R¹⁰ in the generalformula (5) include aryl groups having 6 to 14 carbon atoms, andspecific examples thereof include a phenyl group, a naphthyl group, ananthryl group, a phenanthryl group, a biphenyl group, and the like.Moreover, the examples also include metallocenyl groups such as aferrocenyl group.

Examples of the heterocyclic group represented by R⁸ to R¹⁰ in thegeneral formula (5) include heteromonocyclic or heteropolycyclic groupssuch as a furyl group, a thienyl group, a pyridyl group, a pyrimidinylgroup, a pyrazinyl group, a pyridazinyl group, a pyrazolyl group, animidazolyl group, an oxazolyl group, a thiazolyl group, a benzofurylgroup, a benzothienyl group, a quinolyl group, an isoquinolyl group, aquinoxalinyl group, a phthalazinyl group, a quinazolinyl group, anaphthyridinyl group, a cinnolinyl group, a benzoimidazolyl group, abenzoxazolyl group, and a benzothiazolyl group.

Each of the alicyclic group having 5 to 8 carbon atoms, the aryl groups,and the heterocyclic groups represented by R⁸ to R¹⁰ in the generalformula (5) may have a substituent. Examples of the substituent includealkyl groups, alkoxy groups, aryl groups, heterocyclic groups, and thelike.

Here, examples of the alkyl group as the substituent include linear orbranched alkyl groups having, for example, 1 to 15 carbon atoms,preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbonatoms, and specific examples thereof include a methyl group, an ethylgroup, a n-propyl group, an isopropyl group, a n-butyl group, a s-butylgroup, an isobutyl group, a t-butyl group, a n-pentyl group, a neopentylgroup, a n-hexyl group, and the like.

Examples of the alkoxy group as the substituent include linear orbranched alkoxy groups having, for example, 1 to 6 carbon atoms, andspecific examples thereof include a methoxy group, an ethoxy group, an-propoxy group, an isopropoxy group, a n-butoxy group, a s-butoxygroup, an isobutoxy group, a t-butoxy group, a n-pentyloxy group, aneopentyloxy group, a n-hexyloxy group, and the like.

Examples of the aryl group as the substituent include aryl groupshaving, for example, 6 to 14 carbon atoms, and specific examples thereofinclude a phenyl group, a naphthyl group, an anthryl group, aphenanthryl group, a biphenyl group, and the like.

Examples of the heterocyclic group as the substituent include aliphaticheterocyclic groups and aromatic heterocyclic groups. Examples of thealiphatic heterocyclic groups include 5- to 8-membered, preferably 5- or6-membered monocyclic, polycyclic, or fused polycyclic aliphaticheterocyclic groups which have, for example, 2 to 14 carbon atoms, andwhich contain, as their hetero atoms, at least one, preferably 1 to 3hetero atoms such as nitrogen atoms, oxygen atoms, and sulfur atoms.Specific examples of the aliphatic heterocyclic groups include a2-oxopyrrolidyl group, a piperidino group, a piperazinyl group, amorpholino group, a tetrahydrofuryl group, a tetrahydropyranyl group, atetrahydrothienyl group, and the like. Meanwhile, examples of thearomatic heterocyclic groups include 5- to 8-membered, preferably 5- or6-membered, monocyclic, polycyclic, or fused polycyclic aromaticheterocyclic (heteroaryl) groups which have, for example, 2 to 15 carbonatoms, and which contains, as their hetero atoms, at least one,preferably 1 to 3 hetero atoms such as nitrogen atoms, oxygen atoms, andsulfur atoms. Specific examples of the aromatic heterocyclic groupsinclude a furyl group, a thienyl group, a pyridyl group, a pyrimidinylgroup, a pyrazinyl group, a pyridazinyl group, a pyrazolyl group, animidazolyl group, an oxazolyl group, a thiazolyl group, a benzofurylgroup, a benzothienyl group, a quinolyl group, an isoquinolyl group, aquinoxalyl group, a phthalazinyl group, a quinazolinyl group, anaphthyridinyl group, a cinnolinyl group, a benzoimidazolyl group, abenzoxazolyl group, a benzothiazolyl group, and the like.

When any two of R⁸, R⁹, and R¹⁰ are bonded to each other to form a ring,the ring formed by R⁸ and R⁹, R⁹ and R¹⁰, or R¹⁰ and R⁸, together withthe phosphorus atom to which R⁸, R⁹, and R¹⁰ are bonded may be afour-membered ring, a five-membered ring, or a six-membered ring.Specific examples of the ring include a phosphetane ring, a phospholanering, a phosphorinane ring, a 2,4-dimethylphosphetane ring, a2,4-diethylphosphetane ring, a 2,5-dimethylphospholane ring, a2,5-diethylphospholane ring, a 2,6-dimethylphosphorinane ring, a2,6-diethylphosphorinane ring, and the like.

Examples of the monophosphine compound represented by the generalformula (5) include trimethylphosphine, triethylphosphine,tributylphosphine, triphenylphosphine, tritolylphosphine,tri(3,5-xylyl)phosphine, methyldiphenylphosphine,dimethylphenylphosphine, phenylphosphorane, and the like.

In addition, the homogeneous copper catalyst represented by the generalformula (4) may contain a solvent of crystallization, if needed.Examples of the solvent of crystallization include water, methanol,ethanol, toluene, and the like.

Specific examples of the homogeneous copper catalyst represented by thegeneral formula (4) in the cases where no monophosphine compound iscoordinated to the complex include CuF₂, CuCl, CuCl₂, CuBr, CuBr₂, CuI,CuI₂, CuOTf, Cu(OTf)₂, CuNO₃, Cu(NO₃)₂, and the like.

Meanwhile, specific examples of the homogeneous copper catalystrepresented by the general formula (4) in the cases where monophosphinecompounds are coordinated to the complex include [CuH(PPh₃)]₆, [Cu (NO₃)(PPh₃)₂], [Cu(NO₃)(P(3,5-xyl)₃)₂], [CuCl(PPh₃)₃], [CuF(PPh₃)₃].2EtOH,[Cu(O-t-Bu)(PPh₃)₂], [Cu(OMs)(PPh₃)₂], [Cu(BH₄) (PPh₃)₂], and the like.

In the description above, OTf represents a triflate group, xylrepresents a xylyl group, and OMs represents a mesylate group.

Moreover, other specific examples of the homogeneous copper catalystrepresented by the general formula (4) include homogeneous coppercatalysts described in Reichle, W. T., Inorg. Chim. Acta, 1971, 5, p.325, and the like.

These homogeneous copper catalysts may be used alone or in anappropriate combination with two or more kinds.

As the homogeneous copper catalyst, a commercially available product maybe used. Alternatively, as a homogeneous copper catalyst in which amonophosphine compound is coordinated to the complex, one produced asappropriate by a publicly known method may be used. For example, thehomogeneous copper catalyst may be prepared by the method described in“JIKKEN KAGAKU KOZA (Encyclopedia of Experimental Chemistry), fourthedition,” vol. 18, (organometallic complexes), edited by the ChemicalSociety of Japan. For example, the homogeneous copper catalyst can beobtained by a reaction of a monophosphine compound with CuX, CuX₂, or ahydrate thereof (X has the same meaning as that of X in the generalformula (4)).

Moreover, the homogeneous copper catalyst may be prepared bysubstitution of a homogeneous copper catalyst with a differentsubstituent.

Note that the above-described homogeneous copper catalyst may beprepared in the reaction system at the time of the hydrogenationreaction of the present invention.

In the present invention, the amount of the catalyst used variesdepending on a hydrogenation substrate, which is a raw material,reaction conditions, the kind of the catalyst, and the like, as well ascost effectiveness. However, the amount is generally in the range from0.001 mol % to 10 mol %, preferably 0.01 mol % to 2 mol %, in terms ofmolar ratio of the homogeneous copper catalyst to the hydrogenationsubstrate.

In the present invention, a diphosphine compound is used in the reactionsystem. For example, the diphosphine compound can be represented by thefollowing general formula (1):

(where R¹ to R⁴ each independently represent an alkyl group having 1 to10 carbon atoms, an alicyclic group which has 5 to 8 carbon atoms andwhich may have a substituent, an aryl group which may have asubstituent, or a heterocyclic group which may have a substituent; R¹and R², as well as R³ and R⁴, may be bonded to each other to form aring; and A represents an alkylene chain which may have a substituent, acycloalkanediyl group which may have a substituent, an alaryldiyl groupwhich may have a substituent, or an aryldiyl group which may have asubstituent).

Examples of the alkyl group having 1 to 10 carbon atoms and representedby R¹, R², R³, or R⁴ of the general formula (1) include a linear orbranched alkyl groups having 1 to 10 carbon atoms, and examples thereofinclude a methyl group, an ethyl group, a n-propyl group, an isopropylgroup, a n-butyl group, an-isobutyl group, a s-butyl group, a t-butylgroup, a n-pentyl group, a n-hexyl group, a n-octyl group, and the like.

Examples of the alicyclic group having 5 to 8 carbon atoms andrepresented by R¹, R², R³, or R⁴ of the general formula (1) include acyclopentyl group, a cyclohexyl group, a cycloheptyl group, and thelike.

Examples of the aryl group represented by R¹, R², R³, or R⁴ of thegeneral formula (1) include aryl groups having 6 to 14 carbon atoms, andspecific examples thereof include a phenyl group, a naphthyl group, ananthryl group, a phenanthryl group, a biphenyl group, and the like.Moreover, the examples also include metallocenyl groups such as aferrocenyl group.

Examples of the heterocyclic group represented by R¹, R², R³, or R⁴ ofthe general formula (1) include heteromonocyclic or heteropolycyclicgroups such as a furyl group, a thienyl group, a pyridyl group, apyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a pyrazolylgroup, an imidazolyl group, an oxazolyl group, a thiazolyl group, abenzofuryl group, a benzothienyl group, a quinolyl group, an isoquinolylgroup, a quinoxalinyl group, a phthalazinyl group, a quinazolinyl group,a naphthyridinyl group, a cinnolinyl group, a benzoimidazolyl group, abenzoxazolyl group, and a benzothiazolyl group.

Each of the alicyclic group having 5 to 8 carbon atoms, the aryl group,and the heterocyclic group represented by R¹, R², R³, or R⁴ of thegeneral formula (1) may have a substituent. Examples of the substituentinclude alkyl groups, alkoxy groups, aryl groups, heterocyclic groups,and the like.

Here, examples of the alkyl group as the substituent include linear orbranched alkyl groups having, for example, 1 to 15 carbon atoms,preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbonatoms, and specific examples thereof include a methyl group, an ethylgroup, a n-propyl group, an isopropyl group, a n-butyl group, a s-butylgroup, an isobutyl group, a t-butyl group, a n-pentyl group, a neopentylgroup, a n-hexyl group, and the like.

Examples of the alkoxy group as the substituent include linear orbranched alkoxy groups having, for example, 1 to 6 carbon atoms, andspecific examples thereof include a methoxy group, an ethoxy group, an-propoxy group, an isopropoxy group, a n-butoxy group, a s-butoxygroup, an isobutoxy group, a t-butoxy group, a n-pentyloxy group, aneopentyloxy group, a n-hexyloxy group, and the like.

Examples of the aryl group as the substituent include aryl groupshaving, for example, 6 to 14 carbon atoms, and specific examples thereofinclude a phenyl group, a naphthyl group, an anthryl group, aphenanthryl group, a biphenyl group, and the like.

Examples of the heterocyclic group as the substituent include aliphaticheterocyclic groups and aromatic heterocyclic groups. Examples of thealiphatic heterocyclic groups include 5- to 8-membered, preferably 5- or6-membered, monocyclic, polycyclic, or fused polycyclic aliphaticheterocyclic groups which have, for example, 2 to 14 carbon atoms, andwhich contain, as their hetero atoms, at least one, preferably 1 to 3hetero atoms such as nitrogen atoms, oxygen atoms, and sulfur atoms.Specific examples of the aliphatic heterocyclic groups include a2-oxopyrrolidyl group, a piperidino group, a piperazinyl group, amorpholino group, a tetrahydrofuryl group, a tetrahydropyranyl group, atetrahydrothienyl group, and the like. Meanwhile, examples of thearomatic heterocyclic groups include 5- to 8-membered, preferably 5- or6-membered, monocyclic, polycyclic, or fused polycyclic aromaticheterocyclic (heteroaryl) groups which have, for example, 2 to 15 carbonatoms, and which contain, as their hetero atoms, at least one,preferably 1 to 3 hetero atoms such as nitrogen atoms, oxygen atoms, andsulfur atoms. Specific examples thereof include a furyl group, a thienylgroup, a pyridyl group, a pyrimidinyl group, a pyrazinyl group, apyridazinyl group, a pyrazolyl group, an imidazolyl group, an oxazolylgroup, a thiazolyl group, a benzofuryl group, a benzothienyl group, aquinolyl group, an isoquinolyl group, a quinoxalyl group, a phthalazinylgroup, a quinazolinyl group, a naphthyridinyl group, a cinnolinyl group,a benzoimidazolyl group, a benzoxazolyl group, a benzothiazolyl group,and the like.

When R¹ and R² and/or R³ and R⁴ are bonded to each other to form a ring,the ring formed by R¹ and R² and/or R³ and R⁴ together with thephosphorus atom to which the R¹ and R² and/or R³ and R⁴ are bonded maybe a four-membered ring, a five-membered ring, or a six-membered ring.Specific examples of the ring include a phosphetane ring, a phospholanering, a phosphorinane ring, a 2,4-dimethyl phosphetane ring, a2,4-diethylphosphetane ring, a 2,5-dimethyl phospholane ring, a2,5-diethylphospholane ring, a 2,6-dimethyl phosphorinane ring, a2,6-diethylphosphorinane ring, and the like.

Examples of the alkylene chain represented by A in the general formula(1) include a methylene group, an ethylene group, a trimethylene group,a tetramethylene group, a pentamethylene group, a hexamethylene group,and the like.

Examples of the cycloalkanediyl group represented by A in the generalformula (1) include cyclobutanediyl groups, cyclopentanediyl groups,cyclohexanediyl groups, cycloheptanediyl groups, and the like.

Examples of the alaryldiyl group represented by A in the general formula(1) include a toluene-2,α-diyl group, a 1,2-xylene-α,α′-diyl group, a1,3-xylene-α,α′-diyl group, and the like.

Examples of the aryldiyl group represented by A in the general formula(1) include benzenediyl groups, naphthalenediyl groups, anthracenediylgroups, phenanthrenediyl groups, biphenyldiyl groups, binaphthyldiylgroups, 4,4′-bi (1,3-benzodioxole)diyl group, a ferrocenediyl group, andthe like.

Each of the alkylene chain, the cycloalkanediyl group, the alaryldiylgroup, and the aryldiyl group represented by A in the general formula(1) may have a substituent. Examples of the substituent include alkylgroups, alkoxy groups, aryl groups, heterocyclic groups, and the like.

Here, examples of the alkyl group as the substituent include linear orbranched alkyl groups having, for example, 1 to 15 carbon atoms,preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbonatoms, and specific examples thereof include a methyl group, an ethylgroup, a n-propyl group, an isopropyl group, a n-butyl group, a s-butylgroup, an isobutyl group, a t-butyl group, a n-pentyl group, a neopentylgroup, a n-hexyl group, and the like.

Examples of the alkoxy group as the substituent include linear orbranched alkoxy groups having, for example, 1 to 6 carbon atoms, andspecific examples thereof include a methoxy group, an ethoxy group, an-propoxy group, an isopropoxy group, a n-butoxy group, a s-butoxygroup, an isobutoxy group, a t-butoxy group, a n-pentyloxy group, aneopentyloxy group, a n-hexyloxy group, and the like.

Examples of the aryl group as the substituent include aryl groupshaving, for example, 6 to 14 carbon atoms, and specific examples thereofinclude a phenyl group, a naphthyl group, an anthryl group, aphenanthryl group, a biphenyl group, and the like.

Examples of the heterocyclic group as the substituent include aliphaticheterocyclic groups and aromatic heterocyclic groups. Examples of thealiphatic heterocyclic group include 5- to 8-membered, preferably 5- or6-membered monocyclic, polycyclic, or fused polycyclic aliphaticheterocyclic groups which have, for example, 2 to 14 carbon atoms, andwhich contain, as their hetero atoms, at least one, preferably 1 to 3hetero atoms such as nitrogen atom, oxygen atoms, and sulfur atoms.Specific examples of the aliphatic heterocyclic groups include a2-oxopyrrolidyl group, a piperidino group, a piperazinyl group, amorpholino group, a tetrahydrofuryl group, a tetrahydropyranyl group, atetrahydrothienyl group, and the like. Meanwhile examples of thearomatic heterocyclic groups include 5- to 8-membered, preferably 5- or6-membered monocyclic, polycyclic, or fused polycyclic aromaticheterocyclic (heteroaryl) groups which have, for example, 2 to 15 carbonatoms, and which contain, as their hetero atoms, at least one,preferably 1 to 3 hetero atoms such as nitrogen atoms, oxygen atoms, andsulfur atoms. Specific examples thereof include a furyl group, a thienylgroup, a pyridyl group, a pyrimidinyl group, a pyrazinyl group, apyridazinyl group, a pyrazolyl group, an imidazolyl group, an oxazolylgroup, a thiazolyl group, a benzofuryl group, a benzothienyl group, aquinolyl group, an isoquinolyl group, a quinoxalyl group, a phthalazinylgroup, a quinazolinyl group, a naphthyridinyl group, a cinnolinyl group,a benzoimidazolyl group, a benzoxazolyl group, a benzothiazolyl group,and the like.

Specific examples of the diphosphine compound represented by the generalformula (1) include bis(diphenylphosphino)methane,1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane,1,4-bis(diphenylphosphino)butane, 1,5-bis(diphenylphosphino)pentane,1,6-bis(diphenylphosphino)hexane, 1,2-bis(diphenylphosphino)benzene,1,2-bis(anisylphenylphosphino)ethane, 2,3-bis(diphenylphosphino)butane,1,2-bis(diphenylphosphino)propane,2,3-bis(diphenylphosphino)-5-norbornene,2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane,1-cyclohexyl-1,2-bis(diphenylphosphino)ethane,2,4-bis-(diphenylphosphino)pentane,2,2′-bis(diphenylphosphino)-1,1′-bicyclopentane,2,2′-bis(diphenylphosphino)-1,1′-binaphthyl,2,2′-bis(diphenylphosphino)-1,1′-(5,5′,6,6′,7,7′,8,8′-octahydrobinaphthyl),2,2′-bis(di-p-tolylphosphino)-1,1′-binaphthyl,2,2′-bis(di(3,5-dimethylphenyl)phosphino)-1,1′-binaphthyl,2,2′-bis(diphenylphosphino)-6,6′-dimethyl-1,1′-biphenyl,(4,4′-bi-1,3-benzodioxole)-5,5′-diylbis(diphenylphosphine),(4,4′-bi-1,3-benzodioxole)-5,5′-diylbis[bis(3,5-dimethylphenyl)phosphine],[(4S)-[4,4′-bi-1,3-benzodioxole]-5,5′-diyl]bis[bis[3,5-bis(1,1-dimethylethyl)-4-methoxyphenyl]phosphine],2,2′-bis(diphenylphosphino)benzophenone,2,2′-bis(di(3,5-dimethylphenyl)phosphino)benzophenone, and the like.These diphosphine compounds may be racemic or optically active.

The amount of the diphosphine compound used is 0.1 to 10 equivalent,preferably 1 to 5 equivalent to the copper atoms in the homogeneouscopper catalyst.

The production method of the present invention can be suitably carriedout without any solvent or in a solvent. However, it is preferable touse a solvent. The solvent used is preferably one capable of dissolvingthe hydrogenation substrate and the catalyst, and a single solvent or amixture solvent is used. Specific examples thereof include aromatichydrocarbons such as toluene and xylene; aliphatic hydrocarbons such ashexane and heptane; halogenated hydrocarbons such as methylene chlorideand chlorobenzene; ethers such as diethyl ether, tetrahydrofuran, methylt-butyl ether, and cyclopentyl methyl ether; alcohols such as methanol,ethanol, 1-propanol, 2-propanol, n-butanol, and 2-butanol; polyols suchas ethylene glycol, propylene glycol, 1,2-propanediol, and glycerine;nitriles such as acetonitrile; amides such as N,N-dimethylformamide andN-methylpyrrolidone; amines such as pyridine and triethylamine; and thelike. Of these, alcohols are preferable. Particularly preferable areethanol, 1-propanol and 2-propanol. The amount of the solvent used canbe selected as appropriate depending on reaction conditions and thelike, and may be an amount with which the concentration of the rawmaterial can be 0.05 mol/L to 8.0 mol/L, and preferably 0.8 mol/L to 3.0mol/L. The reaction is performed with stirring, if necessary.

In a preferred embodiment of the production method of the presentinvention, a base can be further added to the reaction system, and thusthe reaction can be performed in the presence of the base. This allowsthe hydrogenation reaction to proceed smoothly. Examples of the baseused and added to the reaction system include organic base compounds andinorganic base compounds.

Specific examples of the above-described organic base compounds used inthe present invention include amines such as triethylamine,diisopropylethylamine, N,N-dimethylaniline, piperidine, pyridine,4-dimethylaminopyridine, 1,5-diazabicyclo[4.3.0]nona-5-ene,1,8-diazabicyclo[5.4.0]undec-7-ene, tri-n-butylamine, andN-methylmorpholine. Of these, triethylamine, diisopropylethylamine, andthe like are particularly preferable.

Examples of the inorganic base compounds used in the present inventioninclude alkali metal carbonates such as potassium carbonate, sodiumcarbonate, lithium carbonate, and cesium carbonate; alkaline earth metalcarbonates such as magnesium carbonate, and calcium carbonate; alkalimetal hydrogen carbonates such as sodium hydrogen carbonate andpotassium hydrogen carbonate; alkali metal hydroxides such as sodiumhydroxide, potassium hydroxide, and lithium hydroxide; alkaline earthmetal hydroxides such as magnesium hydroxide and calcium hydroxide;alkali metal alkoxides such as sodium methoxide, sodium ethoxide, sodiumisopropoxide, sodium t-butoxide, potassium methoxide, potassiumethoxide, potassium isopropoxide, potassium t-butoxide, lithiummethoxide, lithium isopropoxide, and lithium t-butoxide; alkaline earthmetal alkoxides such as magnesium methoxide and magnesium ethoxide; andmetal hydrides such as sodium hydride and calcium hydride. Of these,particularly preferable are sodium carbonate, potassium carbonate,cesium carbonate, sodium t-butoxide, potassium t-butoxide, sodiumhydroxide, potassium hydroxide, and lithium hydroxide.

In the present invention, the amount of the base compound used can beselected as appropriate depending on the catalyst used, reactionconditions, and the like, and is generally 0.1 equivalent to 1,000equivalent, and preferably 1 equivalent to 100 equivalent relative tothe homogeneous copper catalyst. Note that the base compound can beadded, as it is, to the reaction system, or can be added to the reactionsystem as a solution in which the base compound is dissolved in thereaction solvent or the like.

In the present invention, it is also possible to mix one or both of thediphosphine compound and the base with the homogeneous copper catalystin advance, and then use the mixture as the catalyst. Specifically, thediphosphine compound and/or the base are mixed with the homogeneouscopper catalyst in a solvent in advance, and stirring is performed.Then, the residue obtained by evaporating the solvent is added to thereaction system as the catalyst. Alternatively, the residue is dissolvedin a solvent, and then the obtained solution is added to the reaction asthe catalyst. This may lead to improvement in the conversion of thehydrogenation substrate into the alcohol, and improvement in selectivitywhich means the conversion into the desired alcohol.

Moreover, in a preferred embodiment of the production method of thepresent invention, it is possible to perform the production method inthe presence of an additive such as an ammonium salt or a phosphoniumsalt.

Specific examples of the ammonium salt include ammonium chloride,tetrabutylammonium chloride, tetrabutylammonium bromide,tetrabutylammonium fluoride, tetraphenylammonium chloride, and the like.

Specific examples of the phosphonium salt include tetraphenylphosphoniumchloride, tetraphenylphosphonium bromide, and the like.

The amount of the additive used is 0 to 10 equivalent, and preferably0.0001 to 2 equivalent, with respect to the substrate.

Moreover, in a preferred embodiment of the production method of thepresent invention, it is possible to perform the production method whilea monophosphine compound represented by the general formula (5) isfurther added.

The amount of the monophosphine added is generally 0 to 20 equivalent,and preferably 0 to 10 equivalent, with respect to the homogeneouscopper catalyst.

In the present invention, the reaction temperature for performing thehydrogenation reaction is preferably 0° C. to 150° C., and morepreferably 20° C. to 100° C. If the reaction temperature is too low, alarge amount of an unreacted raw material may remain. Meanwhile, if thereaction temperature is too high, the raw material, the catalyst, or thelike may decompose. Hence, both cases are not preferable.

In the present invention, the hydrogen pressure for performing thehydrogenation reaction is preferably 0.1 MPa to 10 MPa, and morepreferably 0.5 MPa to 6 MPa.

Meanwhile, the reaction time is generally about 1 hour to 100 hours, andpreferably 5 hours to 24 hours, in which a sufficiently highraw-material conversion can be achieved. After the reaction iscompleted, a desired alcohol compound can be obtained by one ofgenerally used purification methods such as extraction, filtration,crystallization, distillation, and various kinds of chromatography, orby an appropriate combination thereof.

EXAMPLES

The present invention will be described in detail on the basis ofExamples shown below. However, the present invention is not limited tothese Examples at all. Note that the conversion and the selectivity weredetermined by gas chromatography (GC). The apparatus used andmeasurement conditions were as follows:

GC: GC353B (manufactured by GL Sciences Inc.)

Column: BC-WAX 0.25 mm (I.D.)×30 m (length), 0.250 μm (thickness)[manufactured by GL Sciences Inc.]

Conditions: injection 220° C., detector 250° C.

Column initial temperature: 50° C. (10 min.), Rate of temperature riseof column: 10° C./min., Column final temperature: 230° C. (32 min.)

Note that DPPB represents 1,4-bis (diphenylphosphino) butane.

Meanwhile, S/C represents a molar ratio of the hydrogenation substrateto the catalyst.

Examples 1 to 6 Hydrogenation Reactions of α,β-Unsaturated Aldehydes(S/C=500)

Into a stainless steel autoclave equipped with a glass inner tube, [Cu(NO₃) (PPh₃)₂] (11.7 mg, 0.018 mmol) and DPPB (7.7 mg, 0.018 mmol) wereintroduced. The inside of the autoclave was then replaced with nitrogen.To the autoclave, an ethanolic solution of sodium hydroxide (0.03 M)(6.0 mL, 0.18 mmol) and each α,β-unsaturated aldehyde (9 mmol) wereadded, and stirring was performed at a hydrogen pressure of 5 MPa at 50°C. for 16 hours. The hydrogen was released with great care, and theconversion was analyzed by GC. The contents were concentrated, and thenpurified by silica gel chromatography. Thus, the corresponding alcoholwas obtained. Table 1 shows the substrates, the conversions, and theisolated yields.

TABLE 1 E/Z Isolated (hydrogenation Conver- yield E/Z Example R^(a)R^(b) R^(c) substrate) sion (%) (%) of 1 1/2 1 Ph H Me 99/1 >99 9999/1 >99/1 2 Ph H n-Amyl 95/5 >99 98 95/5 >99/1 3 Ph Ph H N.A. 98 96N.A. >99/1 4 Ph H H >99/1  >99 68 >99/1  >99/1 5 n-Pr H Et 94/6 98 8791/9  16/1 6 Et H Me 99/1 >99 72 97/3  40/1

Example 7 Hydrogenation Reaction of α-Methyl Cinnamic Aldehyde(S/C=1000)

Into a stainless steel autoclave equipped with a glass inner tube,[Cu(NO₃)(PPh₃)₂] (11.7 mg, 0.018 mmol) and DPPB (7.7 mg, 0.018 mmol)were introduced. The inside of the autoclave was then replaced withnitrogen. To the autoclave, an ethanolic solution of sodium hydroxide(0.03 M) (6.0 mL, 0.18 mmol), 6 mL of ethanol, and a-methyl cinnamicaldehyde (E/Z=99/1; 2.52 mL, 18 mmol) were added, and stirring wasperformed at a hydrogen pressure of 5 MPa at 50° C. for 16 hours. Thehydrogen was released with great care, and the conversion was analyzedby GC. The conversion was 98%. The contents were concentrated, and thenpurified by silica gel chromatography. Thus, 2.53 g of the correspondingalcohol was obtained.

Isolated yield: 95%, E/Z(1b)=99/1, 1b/2b=>99/1

Example 8 Hydrogenation Reaction of α-Methyl Cinnamic Aldehyde (UsingCu(NO₃)₂.3H₂O and PPh₃)

Into a stainless steel autoclave equipped with a glass inner tube,Cu(NO₃)₂.3H₂O (3.4 mg, 0.018 mmol), triphenylphosphine (14.2 mg, 0.054mmol), and DPPB (7.7 mg, 0.018 mmol) were introduced. The inside of theautoclave was then replaced with nitrogen. To the autoclave, anethanolic solution of sodium hydroxide (0.03 M) (6.0 mL, 0.18 mmol), 6mL of ethanol, and α-methyl cinnamic aldehyde (E/Z=99/1; 1.26 mL, 9mmol) were added, and stirring was performed at a hydrogen pressure of 5MPa at 50° C. for 16 hours. The hydrogen was released with great care,and the conversion was analyzed by GC. The conversion was 99%. Thecontents were concentrated, and then purified by silica gelchromatography. Thus, the corresponding alcohol was obtained.

Isolated yield: 97%, E/Z(1b)=99/1, 1b/2b=>99/1

Example 9 Hydrogenation Reaction of α-Methyl Cinnamic Aldehyde (Using Cu(NO₃)₂.3H₂O)

Into a stainless steel autoclave equipped with a glass inner tube, Cu(NO₃)₂ (3.4 mg, 0.018 mmol) and DPPB (7.7 mg, 0.018 mmol) wereintroduced. The inside of the autoclave was then replaced with nitrogen.To the autoclave, an ethanolic solution of sodium hydroxide (0.03 M)(6.0 mL, 0.18 mmol) and α-methyl cinnamic aldehyde (E/Z=99/1; 1.26 mL, 9mmol) were added, and stirring was performed at a hydrogen pressure of 5MPa at 50° C. for 16 hours. The hydrogen was released with great care,and the conversion was analyzed by GC. The conversion was 99%. Thecontents were concentrated, and then purified by silica gelchromatography. Thus, the corresponding alcohol was obtained.

Isolated yield: 91%, E/Z(1b)=99/1, 1b/2b=>99/1

Example 10 Hydrogenation Reaction of α-Methyl Cinnamic Aldehyde (Usingn-Butanol Solvent)

Into a stainless steel autoclave equipped with a glass inner tube, [Cu(NO₃) (PPh₃)₂] (11.7 mg, 0.018 mmol) and DPPB (7.7 mg, 0.018 mmol) wereintroduced. The inside of the autoclave was then replaced with nitrogen.To the autoclave, a n-butanol solution of sodium hydroxide (0.03 M) (6.0mL, 0.18 mmol) and α-methyl cinnamic aldehyde (E/Z=99/1; 1.26 mL, 9mmol) were added, and stirring was performed at a hydrogen pressure of 5MPa at 50° C. for 16 hours. The hydrogen was released with great care,and the conversion was analyzed by GC. The conversion was 99%.

Example 11 Hydrogenation Reaction of α-Methyl Cinnamic Aldehyde (Usingtert-Butanol Solvent)

Into a stainless steel autoclave equipped with a glass inner tube,[Cu(NO₃) (PPh₃)₂](11.7 mg, 0.018 mmol) and DPPB (7.7 mg, 0.018 mmol)were introduced. The inside of the autoclave was then replaced withnitrogen. To this autoclave, a tert-butanol solution of sodium hydroxide(0.03 M) (6.0 mL, 0.18 mmol) and α-methyl cinnamic aldehyde (9 mmol)were added, and stirring was performed at a hydrogen pressure of 5 MPaat 50° C. for 16 hours. The hydrogen was released with great care, andthe conversion was analyzed by GC. The conversion was 99%.

Example 12 Hydrogenation Reaction of2-Ethyl-4-(2,2,3-trimethylcyclopento-3-ene-1-yl)-2-buten-1-al

Into a stainless steel autoclave equipped with a glass inner tube, [Cu(NO₃) (PPh₃)₂] (11.7 mg, 0.018 mmol) and DPPB (7.7 mg, 0.018 mmol) wereintroduced. The inside of the autoclave was then replaced with nitrogen.To the autoclave, an ethanolic solution of sodium hydroxide (0.03 M)(6.0 mL, 0.18 mmol) and2-ethyl-4-(2,2,3-trimethylcyclopento-3-ene-1-yl)-2-buten-1-al (E/Z=93/7;2.02 mL, 9 mmol) were added, and stirring was performed at a hydrogenpressure of 5 MPa at 50° C. for 16 hours. The hydrogen was released withgreat care, and the conversion was analyzed by GC. The conversion was98%. The contents were concentrated, and then purified by silica gelchromatography. Thus, 1.76 g of the corresponding alcohol was obtained.

Isolated yield: 94%, E/Z(1c)=96/4, 1c/2c=35/1

Example 13 Hydrogenation Reaction of Perillaldehyde (S/C=500)

Into a stainless steel autoclave equipped with a glass inner tube,[Cu(NO₃)(PPh₃)₂] (11.7 mg, 0.018 mmol) and DPPB (7.7 mg, 0.018 mmol)were introduced. The inside of the autoclave was then replaced withnitrogen. To the autoclave, an ethanolic solution of sodium hydroxide(0.03 M) (6.0 mL, 0.18 mmol) and perillaldehyde (2.02 mL, 9 mmol) wereadded, and stirring was performed at a hydrogen pressure of 5 MPa at 50°C. for 16 hours. The hydrogen was released with great care, and theconversion was analyzed by GC (>99%). The contents were concentrated,and then purified by silica gel chromatography. Thus, 1.26 g of thecorresponding alcohol was obtained.

Isolated yield: 92%, 1d/2d=52/1

Comparative Example 1 Hydrogenation Reaction of Perillaldehyde (inaccordance with the Method in Non-Patent Document 4; Amount of CatalystUsed: 0.2 mol %)

Into a stainless steel autoclave equipped with a glass inner tube,[CuH(PPh₃)]₆ (16.3 mg, 0.05 mmol; in terms of Cu) was introduced. Theinside of the autoclave was then replaced with nitrogen. To thisautoclave, toluene (17.0 mL), tert-butyl alcohol (0.19 mL, 2.0 mmol),dimethylphenylphosphine (43 μl, 0.3 mmol), and perillaldehyde (3.89 mL,25 mmol) were added, and stirring was performed at a hydrogen pressureof 5 MPa at 30° C. for 16 hours. The hydrogen was released with greatcare, and the conversion was analyzed by GC. The conversion was lessthan 1%.

Example 14 Hydrogenation Reaction of 3-(2-Furyl)-acrolein

Into a stainless steel autoclave equipped with a glass inner tube,[Cu(NO₃)(PPh₃)₂] (11.7 mg, 0.018 mmol), DPPB (7.7 mg, 0.018 mmol) and3-(2-furyl)-acrolein (E/Z=>99/1, 1.24 g, 9 mmol) were introduced. Theinside of the autoclave was then replaced with nitrogen. To theautoclave, an ethanolic solution of sodium hydroxide (0.03 M) (6.0 mL,0.18 mmol) was added, and stirring was performed at a hydrogen pressureof 5 MPa at 50° C. for 16 hours. The hydrogen was released with greatcare, and the conversion was analyzed by GC (>99%). The contents wereconcentrated, and then purified by silica gel chromatography. Thus, 1.15g of the corresponding alcohol was obtained.

Isolated yield: 91%, E/Z(1e)=>99/1, 1e/2e=>99/1

Example 15 Hydrogenation Reaction of 3-(2-Furyl)-acrolein (with[CuH(PPh₃)]₆)

Into a stainless steel autoclave equipped with a glass inner tube,[CuH(PPh₃)]₆ (5.9 mg, 0.018 mmol; in terms of Cu), DPPB (7.7 mg, 0.018mmol) and 3-(2-furyl)-acrolein (E/Z=>99/1, 1.24 g, 9 mmol) wereintroduced. The inside of the autoclave was then replaced with nitrogen.To the autoclave, an ethanolic solution of sodium hydroxide (0.03 M)(6.0 mL, 0.18 mmol) was added, and stirring was performed at a hydrogenpressure of 5 MPa at 50° C. for 15 hours. The hydrogen was released withgreat care, and the conversion was analyzed by GC (>99%). The contentswere concentrated, and then purified by silica gel chromatography. Thus,1.21 g of the corresponding alcohol was obtained.

Isolated yield: 96%, E/Z(1e)=>99/1, 1e/2e=>99/1

Examples 16 to 23 Hydrogenation Reactions of Aldehydes

Into a stainless steel autoclave equipped with a glass inner tube, [Cu(NO₃) (PPh₃)₂] (11.7 mg, 0.018 mmol) and DPPB (7.7 mg, 0.018 mmol) wereintroduced. The inside of the autoclave was then replaced with nitrogen.To the autoclave, an ethanolic solution of sodium hydroxide (0.03 M)(6.0 mL, 0.18 mmol) and each aldehyde (9 mmol) were added, and stirringwas performed at a hydrogen pressure of 5 MPa at 50° C. for 16 hours.The hydrogen was released with great care, and the conversion wasanalyzed by GC. The contents were concentrated, and then purified bysilica gel chromatography. Thus, the corresponding alcohol was obtained.Table 2 shows the substrates, the conversions, and the isolated yields.

TABLE 2 Conversion Isolated yield Example R (%) (%) 16 Ph >99 91 173,4-Methylenedioxyphenyl >99 98 18 2-(5-Methylfuryl) >99 87 192-Thienyl >99 96 20 3-Pyridyl >99 85 21 1-Phenylethyl >99 76 222-Phenylethyl  88 10 23 cyclohexyl >99 90

The invention claimed is:
 1. A method for producing an alcohol compound,said method comprising performing a hydrogenation reaction of analdehyde compound of the following general formula (3):

wherein R⁵ to R⁷ each independently represent a hydrogen atom, an alkylgroup which has 1 to 10 carbon atoms and which may have a substituent,an alkenyl group which may have a substituent, an alicyclic group whichhas 5 to 8 carbon atoms and which may have a substituent, an aryl groupwhich may have a substituent, or a heterocyclic group which may have asubstituent; and R⁵ and R⁶ and/or R⁵ and R⁷, may be bonded to each otherto form a ring, in the presence of a homogeneous copper catalyst and adiphosphine compound of the following general formula (1):

wherein R¹ to R⁴ each independently represent an alkyl group having 1 to10 carbon atoms, an alicyclic group which has 5 to 8 carbon atoms andwhich may have a substituent, an aryl group which may have asubstituent, or a heterocyclic group which may have a substituent; R¹and R² and/or R³ and R⁴, may be bonded to each other to form a ring; andA represents an alkylene chain which may have a substituent, acycloalkanediyl group which may have a substituent, an alaryldiyl groupwhich may have a substituent, or an aryldiyl group which may have asubstituent.
 2. The production method according to claim 1, wherein thehydrogenation reaction of the aldehyde compound is performed in thepresence of the homogeneous copper catalyst, the diphosphine compound,and an alcohol.